Diamine terminated primary amine-aldehyde sulfur converting compositions and methods for making and using same

ABSTRACT

A new class of sulfur scavenging or converting compositions is disclosed comprising diamine terminated, amine-aldehyde adducts, where the adducts are substantially bimolecular amine-aldehyde adducts and the composition is substantially free of trimer and/or triazines. Methods for making and using the new class of sulfur scavenging or converting composition are also disclosed.

RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 10/734,600, filed 12 Dec. 2003.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel sulfur scavenger including adiamine terminated reaction product of a primary amine and an aldehydeunder conditions to reduce or preclude triazine formation.

More particularly, the present invention relates a novel sulfurscavenger including a diamine terminated reaction product of a primaryamine and an aldehyde, where at least one aldehyde is added to asolution of at least one alkylamine under conditions to reduce orpreclude triazine formation to produce a sulfur scavenging compositionthat does not liberate aldehyde upon heating and where trace imines arechemically reduced by added a reducing agent to the crude product priorto workup.

2. Description of the Related Art

Noxious sulfur species, such as hydrogen sulfide and thiols, are presentin many industrial and waste management environments such as oil and gasproduction, refining, chemical processing and manufacturing, coalgasification, sewage treatment and other industrial and waste managementprocess. Many compounds have been prepared and patented to reduce thesenoxious sulfur species converting them to higher molecular weight sulfurcontaining materials, many of which are water soluble or have a higherpartition coefficient for water than hydrocarbon. Such scavengers aredisclosed in U.S. Pat. Nos. 4,748,011; 4,978,512; 4,748,011; 4,978,512;2,390,153; 3,856,921; 4,112,050; 4,112,051; and 4,112,052. Many of thesecompositions also have utility in converting other troublesome compoundssuch as carbon dioxide into more benign compounds. See “StericallyHindered Amines for CO₂ Removal from Gases” in I & EC FUNDAMENTALS, Vol.2, No. 22 (1983).

Although many sulfur scavengers have been prepared and used in theseindustrial and water management applications, there is still a need inthe art for compositions to reduce, reduce to a desired level oreliminate noxious sulfur agents or other troublesome compounds that arethermally stable, contain little or no triazines or other compounds thatare known to liberate aldehyde upon heating and have acceptableproperties for use in capillary coiled tubing applications, applicationwhere small diameter tubing it inserted into a well to a given depth andchemical agents such as sulfur scavengers are injected into the wellfluid through the tubing.

SUMMARY OF THE INVENTION

The present invention provides a sulfur scavenging composition includinga diamine centered, oligomer or polymer of a bimolecular adduct ofprimary amines and aldehydes, where the composition preferably includessufficient diamine so that the composition liberates little or noaldehyde upon heating and where the composition have a pH between about9 and about 13, and preferably, between about 10 and about 12.5.

The present invention also provides a sulfur scavenging compositionincluding oligomers and/or polymers formed by reacting a diamine and aprimary amine-aldehyde reaction product, where the reaction productcomprises substantially biomolecular adducts of primary aminesaldehydes, where the composition preferably includes sufficient diamineso that the composition liberates little or no aldehyde upon heating andincludes no or only trace amount of triazines.

The present invention also provides a sulfur scavenging compositionincluding a compound of formula (I):

where R is an alkenyl group having between about 1 and about 20 carbonatoms, where one or more of the carbon atoms can be oxygen atoms in theform of ether, hydroxy and/or carboxy moieties and/or nitrogen atoms inthe form of tertiary amine and/or amide moieties, R′ and R″ are the sameor different carbon-containing groups having between about 1 and about20 carbon atoms, where one or more of the carbon atoms can be oxygenatoms in the form of ether, hydroxy, and/or carboxy moieties and/ornitrogen atoms in the form of tertiary amine and/or amide moieties,where k, l, m and n are integers having a value between 0 and 2,provided that at least one have a have of 1 or 2, where the compositionpreferably liberates little or no aldehyde upon heating and includes noor only trace amounts of triazines.

The present invention provides a method for preparing sulfur scavengingcompositions including the steps of adding at least one aldehyde to asolution including at least one primary amine under conditions to reduceor eliminate triazine formation and adding to the reaction at least onediamine. Preferably, the diamine is added in an amount sufficient toreduce or substantially eliminate liberation of aldehyde upon heating.The method can optionally include the step of hydrogenating any imineproducts to their corresponding saturated analog through the addition ofa reducing agent such as sodium borohydride.

The present invention provides a method for converting noxious sulfurspecies to high molecular weight sulfur species including the steps ofcontacting a fluid or fluid stream including noxious sulfur species withan effective amount of a sulfur scavenging or converting compositionincluding a compound of formula (I):

where R is an alkenyl group having between about 1 and about 20 carbonatoms, where one or more of the carbon atoms can be oxygen atoms in theform of ether, hydroxy and/or carboxy moieties and/or nitrogen atoms inthe form of tertiary amine and/or amide moieties, R′ and R″ are the sameor different carbon-containing groups having between about 1 and about20 carbon atoms, where one or more of the carbon atoms can be oxygenatoms in the form of ether, hydroxy and/or carboxy moieties and/ornitrogen atoms in the form of tertiary amine and/or amide moieties,where k, l, m and n are integers having a value between 0 and 2,provided that at least one have a have of 1 or 2, where the compositionpreferably liberates substantially no aldehyde upon heating and includesno or only trace amounts of triazines, where the amount is sufficient toreduce, to reduce below a target level or to substantially eliminate thenoxious sulfur species. By fluid the inventors means any combination ofmaterial including liquids, gases and/or solids that will flow at aparticular operating temperature.

The present invention provides a method comprising the step of injectinginto a fluid or fluid stream of a gas or oil production wellhead, aflowline, a separator, a tank, a line heater, a heater treater, orsimilar gas or oil handling and/or processing equipment an effectiveamount of a composition of this invention or a solution including acomposition of this invention, where the amount is sufficient to reduce,reduce below a desired level or substantially eliminate noxious sulfurspecies in the fluid or fluid stream. The injecting step can beperformed by chemical injection pumps, overpressure from a storagevessel with fluid or gas to facilitate entrance into sulfur containingfluid or fluid stream. The injecting step can also include passing thecomposition or solution containing the composition through an atomizeror nebulizer to finely distribute the composition or solution into thefluid or fluid stream. The injection step can be a single point or portinjection format or preferably a multi-point or multi-port injectionformat, i.e., the composition or solution including the composition isintroduced into the fluid or stream at multiple locations to improvesulfur conversion efficiency and effectiveness.

DESCRIPTION OF THE DRAWINGS

The invention can be better understood with reference to the followingdetailed description together with the appended illustrative drawings inwhich like elements are numbered the same:

FIG. 1 depicts a plot of weekly average water production (M3/day) versesproduction week evidencing the effect of using a composition of thisinvention after optimization (adjusting amount bases on noxious sulfurcontent) and after multi-point injection of the composition into wellfluids;

FIG. 2 depicts a plot of average weekly cost/BOE verses production weekevidencing the effect of using a composition of this invention afteroptimization (adjusting amount bases on noxious sulfur content) andafter multi-point injection of the composition into well fluids;

FIG. 3 depicts a plot of composition usage in litres/day versesproduction week evidencing the effect of using a composition of thisinvention after optimization (adjusting amount bases on noxious sulfurcontent) and after multi-point injection of the composition into wellfluids;

FIG. 4 depicts a plot of composition usage in litres/day versesproduction week evidencing the effect of using a composition of thisinvention after optimization (adjusting amount bases on noxious sulfurcontent) and after multi-point injection of the composition into wellfluids;

FIG. 5 depicts a plot of MMSCF and L/MMSCF verses production weekevidencing the effect of using a composition of this invention afteroptimization (adjusting amount bases on noxious sulfur content) andafter multi-point injection of the composition into well fluids;

FIG. 6 depicts a plot of composition usage (L/Day) verses productionweek evidencing the effect of using a composition of this inventionafter optimization (adjusting a mount bases on noxious sulfur content)and after multi-point injection of the composition into well fluids; and

FIG. 7 depicts a plot of composition usage (L/Day) verses productionweek evidencing the effect of using a composition of this inventionafter optimization (adjusting amount bases on noxious sulfur content)and after multi-point injection of the composition into well fluids.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have found that a sulfur scavenging composition can beprepared by contacting at least one amine with at least one aldehydeunder reaction conditions designed to reduce or eliminate triazineformation and terminating the reaction by the addition of at least onediamine, where the composition does not liberate aldehyde upon heating.The new sulfur scavenging compositions are ideally suited for convertingnoxious sulfur agents such as hydrogen sulfide, thiols or the likepresent in aqueous or non-aqueous fluid streams such ashydrocarbon-containing liquid, gas or mixed streams into water solublecompositions and for reducing below a given level or eliminating noxioussulfur compounds such as hydrogen sulfide (H₂S), thiol (R^(a)SH), orother odorous and/or corrosive sulfur-containing compounds.

The present invention broadly relates to sulfur scavenging compositionsincluding diamine terminated bimolecular primary amine-aldehyde adduct,where the compositions do not liberate aldehyde upon heating andincludes no or minimal amount of triazines.

The present invention broadly relates to sulfur scavenging compositionsincluding a compound of formula (I):[H_(k)(R″N—R′HC)][H₁(R″N—R′HC)]N—R—N[(CHR′—NR″)_(m)H][(CHR′—NR″)_(n)H]  (I)where R is an alkenyl group having between about 1 and about 20 carbonatoms, where one or more of the carbon atoms can be oxygen atoms in theform of ether, hydroxy, and/or carboxy moieties and/or nitrogen atoms inthe form of tertiary amine and/or amide moieties, R′ and R″ are the sameor different carbon-containing groups having between about 1 and about20 carbon atoms, where one or more of the carbon atoms can be oxygenatoms in the form of ether moieties and/or nitrogen atoms in the form oftertiary amine moieties or amide moieties, where k, l, m and n areintegers having a value between 0 and 2, provided that at least one havea have of 1 or 2, where the composition does not liberate aldehyde uponheating and includes no or only trace amounts of triazines.

The present invention broadly relates to a method for preparing sulfurscavenging compositions including the steps of adding, under controlledconditions, at least one aldehyde or aldehyde donor to a solution of atleast one primary amine under conditions to minimize trimer formation, atriazine precursor and to minimize aldol condensation and thenterminating the reaction product with at least one diamine to producediamine terminated amine-aldehyde oligomers and/or polymers which arethermally stable against aldehyde liberation, i.e., do not liberatealdehyde upon heating. Preferably, the diamine is present an amountsufficient to reduce, to reduce below a given level or substantiallyeliminate the liberation of aldehyde upon heating, where substantiallyeliminate means that the amount of liberated aldehyde is below thedetection limit of a given aldehyde detector. Generally, the amount ofdiamine is between about 1 wt. % and about 25 wt. %, preferably, betweenabout 2 wt. % and about 20 wt. %, particularly, between about 4 wt. %and about 20 wt. %. Of course, the exact amount will depend on thecomposition of the amine-aldehyde reaction product and the nature of thediamine or diamine mixture used to terminate the reaction product.

The present invention broadly relates to a method treating fluidscontaining noxious sulfur species including the steps of contacting thefluid with an effective amount of a sulfur scavenging composition ofthis invention singly, periodically or continuously to convert thenoxious sulfur agents into a high molecular weight sulfur-containingadduct of the sulfur scavenging composition, preferably, a water solublesulfur-containing adduct. The method can also include the steps ofmeasuring a concentration of the noxious sulfur species in the fluid andadded a concentration of the composition in excess of one to one,preferably two to one or more and then reducing the amount ofcomposition until a desired level of noxious sulfur species is measuredin the fluid. Of course, the latter step are associated with continuousapplication of the composition to the fluids.

The present invention provides a method comprising the step of fillingor partially filling a bubble or percolating tower or vessel with afluid and added to the fluid an effective amount of a composition ofthis invention or solution including a composition of this invention,where fluid is static or circulating countercurrent flow to gaspercolating up from bottom of fluid column, and exiting through top ofthe tower or vessel(s) and where the effective amount is sufficient toreduce, reduce to a desired level or substantially eliminate noxioussulfur species in the fluid and/or gas during the percolation step.

The present invention provides a method comprising the step ofcontacting a fluid with an effective amount of a composition of thisinvention or solution including a composition of this invention, wherethe effective amount is sufficient to reduce, reduce to a desired levelor substantially eliminate noxious sulfur species in the fluid. Thefluid can be selected from the group consisting of natural gas, naturalgas liquids, compressed liquids, crude oil, refined oils, refined oilproducts, oil/gas production associated water, other similar fluids andmixtures or combinations.

The present invention provides a method comprising the step of adding aneffective amount of a composition of this invention or a solutionincluding a composition of this invention to a fluid containing noxioussulfur species (H₂S/mercaptans or other sulfur compounds), where thefluid is a gas and/or liquid derived from a refinery, an industrialfacility (chemical processing or the like) or a waste managementfacility such as sewage system off gas, bio-gas from composting, gasesfrom land fills, etc. and where the effective amount is sufficient toreduce, reduce to a desired level or reduce the noxious sulfur speciesbelow a detectable level or to substantially eliminate the sulfurspecies.

The present invention provides a method comprising the step of adding aneffective amount of a composition of this invention or a solutionincluding a composition of this invention to a fluid containing noxioussulfur species (H₂S/mercaptans or other sulfur compounds), where thefluid is gases or liquids from coal bed methane recovery, or generationof gas from coal or syngas preparation and where the effective amount issufficient to reduce, reduce to a desired level or reduce the noxioussulfur species below a detectable level or to substantially eliminatethe sulfur species.

The present invention provides a method comprising the step of adding aneffective amount of a composition of this invention or a solutionincluding a composition of this invention to a fluid containing noxioussulfur species (H₂S/mercaptans or other sulfur compounds) to treat orsweeten the fluid, where the fluid comprises gas storage wells intowells as stored, during storage, and upon gas withdrawal and where theeffective amount is sufficient to reduce, reduce to a desired level orreduce the noxious sulfur species below a detectable level or tosubstantially eliminate the sulfur species.

The present invention provides a method comprising the step of treatingan refinery overhead streams including noxious sulfur species such asH₂S with an effective amount of a composition of this invention or asolution including a composition of this invention, where the effectiveamount is sufficient to reduce, reduce to a desired level or reduce thenoxious sulfur species below a detectable level or to substantiallyeliminate the sulfur species.

The present invention provides a method comprising the step of treatingvapor areas of movable storage vessels such as barges or ships whichcontain vapors including noxious sulfur species such as H₂S thataccumulate during transit with an effective amount of a composition ofthis invention or a solution including a composition of this invention,where the effective amount is sufficient to reduce, reduce to a desiredlevel or reduce the noxious sulfur species below a detectable level orto substantially eliminate the sulfur species.

The reaction products of this invention can be characterized by thefollowing reaction scheme:

R′—CHO+R″NH₂→R′—CH═NR″+minor reaction products

R′—CH═NR″+diamine→diamine-amine-aldehyde oligomers and/or polymers

where R′ and R″ are as described above.

The compositions of this invention have increased efficiencies ascompared to compositions including triazine analogs or imine analogs.The compositions of this invention are well suited for capillary coiledtubing down hold applications. The compositions of this invention arebest used by adjusting the amount utilized until a concentration of thecomposition is about twice the amount of noxious sulfur species in thefluid and then reducing the amount added, while maintaining theconversion efficiency. The compositions of this invention also have agood tri-phasic partitioning property. Unlike many competitive product,the compositions of the present invention partition into the gas phase,hydrocarbon phase and aqueous phase with sufficient partitioningconcentration to reduce, reduce to a given level or substantiallyeliminate (reduce below a given detectable limit) noxious sulfurspecies. Thus, unlike many competitive produce, the present compositionsdo not migrate substantially or totally to the aqueous phase, increasingthe concentration of the composition at the hydrocarbon (organicphase)/gas interface. The tri-phasic behavior of the compositions ofthis invention make them ideally suited for multi-phase applications.Generally, the compositions of this invention are used as a solution ofat least one compound of formula (I) in a solvent. The solutiongenerally includes between about 0.5 ppm and about 500 ppm of the atleast one compound of formula (I), preferably, between about 1 ppm and100 ppm of the at least one compound of formula (I), particularly,between about 1 ppm and 50 ppm of the at least one compound of formula(I), more particularly, between about 1 ppm and 25 ppm of the at leastone compound of formula (I), and especially between about 1 ppm andabout 10 ppm relative to the solvent. Of course, greater and lesseramounts of the compounds of formula (I) can be used depending on theconcentration of noxious sulfur species in the fluid to be treated aswell as on other physical and chemical conditions such as temperature,volume, pressure, Alternatively, Typical application ratios for thecompositions disclosed herein are from about 1 ppm to about 10 ppm,preferably, from about 2 ppm to about 4 ppm of sulfur scavengingcomposition per ppm of hydrogen sulfide in the fluid to be treated. Thisimproved conversion allows more complete removal of hydrogen sulfide ata minimal cost, often without the need for a scrubber tower, whichfurther reduces related equipment costs. The present compositions areactive in two and three phase applications (two liquid phase and one gasphase).

Suitable primary amines for use in the preparation of the sulfurscavenging compositions of this invention include, without limitation, aprimary amine of the formula R″NH₂ where R″ is a linear or branchedalkyl, aryl, alkaryl, or aralkyl group having between about 1 and about20 carbon atoms and where one or more of the carbon atoms can bereplaced by an oxygen atom or a nitrogen atom or nitrogen containinggroup provided that the oxygen atoms are in the form of ether, hydroxyand/or carboxy moieties and the nitrogen atoms are in the form oftertiary amine and/or amide moieties and one or more of the hydrogenatoms can be replaced by a fluorine atom or chlorine atom. Thus, the R″group can include one or more methylene oxide or ethylene oxide moietiesin the carbon chain or one or more tertiary amine moieties in the carbonchain. Preferred R″ groups include, without limitation, methyl, ethyl,propyl, isopropyl, butyl, sec-butyl, isobutyl, hexyls (linear orbranched), hepyls, octyls, nonyls, decyls, phenyl, benzyl, methylsubstituted phenyls, or mixtures or combinations thereof. Exemplaryprimary amines include, without limitation, methylamine, ethylamine,propylamine, isopropylamine, butylamine, sec-butylamine, iso-butylamine,hexylamines (all conformational types), heptylamines (all conformationaltypes), octylamines (all conformational types), nonylamines (allconformational types), decylamines (all conformational types), etc. ormixtures or combinations thereof.

Suitable diamines and triamines for use in the preparation of the sulfurscavenging compositions of this invention include, without limitation,alkyl diamines, cycloalkyl diamines, alkacycloalkyl diamines, aralkyldiamines, aryl diamines, alkaryl diamines, amines heads or the like andanalogs thereof and where one or more of the carbon atoms can bereplaced with nitrogen atoms, oxygen atoms, or mixtures thereof wherethe oxygen atoms form carboxy, hydroxy and or ether moieties and thenitrogen atoms form tertiary amine and/or amide moieties and/or one ormore hydrogen atoms can be replaced with fluorine atoms, chlorine atomsor mixture thereof and including between 2 and about 20 carbon atoms,preferably, about 3 to about 15 carbon atoms and particularly, about 4to about 10 carbon atoms. Exemplary examples of alkyl diaminesincluding, without limitation, 1,2-diaminoethane (1,2-ethylene diamine),1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane,1,3-diaminobutane, 1,4-diaminobutane, 1,2-diaminopentane,1,3-diaminopentane, 1,4-diaminopentane, 1,5-diaminopentane, and similarhigher diaminoalkanes, aminomethylcyclopentylamine,1,2-cyclopentanediamine, 1,6-hexanediamine, 1,2-diaminobenzene, lysine(or other diamine amino acids), 1,2-diaminobenzene, 1,4-diamine benzene,1,2-diphenyl-1,2-ethane diamine, phenylene diamine, 2-hydroxypropylenediamine, hydantoin, N,N-Bis(dihydroxyethyl)ethylenediamine,hexahydrotriazine, aminoethylpiperazine (AEP) or the like, or mixturesor combinations thereof. Amine heads is commercially available fromMonsanto Company and DuPont as a byproduct in the manufacture ofhexamethylenediamine. Although the above listed aliphatic diamines aresuitable for use in making the compositions of the invention, it shouldbe understood that other diamines or triamines can be used as well.Examples of other aliphatic diamines and triamines that can besatisfactorily used in making the subject compositions includebis-hexamethylenetriamine.

As used herein, the term “amine heads” refers to an unrefined mixture ofalkyl diamines that comprise from 4 to 6 carbon atoms. Examples of alkyldiamines typically found in amine heads includeaminomethylcyclopentylamine; 1,2-cyclohexanediamine(1,2-diaminocyclohexane); 1,5-pentanediamine, 2-methyl;1,6-hexanediamine; 1H-azepine, hexahydro; and 1,4-butanediamine. Amineheads is commercially available from Monsanto Company and DuPont as abyproduct in the manufacture of hexamethylenediamine.

Although amine heads is a convenient and useful source of aliphaticdiamines suitable for use in making the compositions of the invention,it should be understood that other diamines or triamines not present inamine heads can likewise be used within the scope of the invention.Examples of other aliphatic diamines and triamines that can besatisfactorily used in making the subject compositions include1,4-diaminocyclohexane and bis-hexamethylenetriamine.

Suitable diamines for use in this invention can also include, withoutlimitation, diamines of the general formulaH₂N—R—NH₂where R is linear or branched alkenyl groups having between about 1 andabout 20 carbon atoms, cycloalkenyl groups having between about 1 andabout 20 carbon atoms, alkylcycloalkenyl groups having between about 1and about 20 carbon atoms, alka arenyl group having between about 1 andabout 20 carbon atoms, ara alkenyl group having between about 1 andabout 20 carbon atoms, or the like or mixtures or combinations thereof.Preferred alkenyl groups have between about 1 and about 10 carbon atoms.The R group can also include atoms other than carbon and hydrogen suchas oxygen, nitrogen, fluorine and/or chlorine. Preferred groupsincluding oxygen atoms in the form of hydroxy or ether moieties ornitrogen atoms in the form of tertiary amine or amide moieties.

Suitable aldehydes useful for making the subject compositions of thisinvention include, without limitation, aldehydes having the formulaR′—CHO or aldehyde donors that generate such aldehydes, where R′ is ahydrogen atom (H) or a linear or branched alkyl, aryl, alkaryl, oraralkyl group having between about 1 and about 20 carbon atoms and caninclude atoms other than carbon and hydrogen such as oxygen, nitrogen,fluorine and/or chlorine, provided that the oxygen atoms are in the formof ether or hydroxy moieties and nitrogen atoms in the form of tertiaryamine and amide moieties. Thus, the R′ group can include one or moremethylene oxide or ethylene oxide moieties in the carbon chain or one ormore tertiary amine or amide moieties in the carbon chain. Preferred R′groups include, without limitation, methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, isobutyl, hexyls (linear or branched), hepyls, octyls,nonyls, decyls, phenyl, benzyl, methyl substituted phenyls, or mixturesor combinations thereof. Exemplary examples of aldehydes include,formaldehyde, paraformaldehyde, arylaldehydes, methoxyaldehydes,hydroxyaldehydes or aldols such as cinnaminaldehyde, glyceraldehydes,acetadol, paraldehyde (trimer of acetaldehyde), vanillin,veratraldehyde, alloxan, noneal, 1-formyl piperdine, salicylaldehyde,citronella or the like, or mixtures or combinations thereof. Preferredexamples of aldehydes useful in this invention, include, withoutlimitation, monoaldehydes having from 1 to 10 carbon atoms (one or morecarbon atoms can be a non-carbon atoms including oxygen or nitrogen andcan include fluorine and/or chlorine hydrogen substitutions) such asparaformaldehyde, formaldehyde, acetaldehyde, glycolaldehyde,glyceraldehyde, hydroxymethyl glyceraldehyde, glyoxal, and methylformcel (a hemi-acetal, 55 percent formaldehyde solution in methanol andmethoxy-methanol or water), aldols, or the like.

Aldehyde donors believed useful in making the compositions of theinvention are preferably selected from the group consisting ofhydantoin; hexamethylenetetramine; hexamethylolmelamine;2-[(hydroxymethyl)amino]ethanol; 5,5-dimethylhydantoin;tris(hydroxymethyl)nitromethane; 2-nitro-2-methyl-1-propanol;2-nitro-2-ethyl-1,3-propanediol; 2-nitro-1-butanol; and acetaldehydeammonia.

Solvent systems comprising up to about 90 weight percent solvent inconjunction with the inventive compositions made by reacting primaryamines with aldehydes under conditions to reduce or eliminate trimerand/or triazine formation followed by reaction termination with at leastone diamine to form an oligomeric and/or polymeric diamine terminatedamine-aldehyde compositions can be used as well. The presence ofsolvents in the reaction mixture during the reaction of amine andformaldehyde, for example, can reduce the formation of undesirablebyproducts. Preferred solvents for use in the reaction system aremethanol, methoxymethanol, diglymine, and mixtures thereof.

The solvents identified below are believed to be exemplary of thosesolvents that can enhance the efficiency of the subject compositions invarious applications: water or methanol, or mixtures thereof;methoxymethanol or mixtures of methoxymethanol and methanol;dicyclopentadiene; formamide; solutions of oxo-alcohols and oxo-alcoholethers; disulfide oil; glycols; excess polyfunctional amines such asdiamines and triamines; terpenes; cyclohexene; d-limonene; m-pyrol;diglymine; neopentyl glycol; glycerin diglymine; and neopentyl glycoland glycerin or glycerol. A solvent such as Texaco Amine C-6 (comprisingmorpholine residues) or methyldiethanolamines or oligomers thereof canbe used in place of diamines to suppress cross-linking, but do notremove free formaldehyde.

The use of catalysts in the compositions of the invention can bedesirable for extending their useful conversion life, for improving theconversion of organic sulfides to a less noxious form, and forconverting low molecular weight sulfide reaction products to higheroxidative forms. In most cases the use of up to about 5 weight percentcatalyst in the reactive mixtures by which the subject compositions areproduced is believed to be satisfactory for achieving the purposesdescribed above.

Catalysts believed to be satisfactory for use in making the compositionsof the invention include, for example, potassium or sodium borohydridein aqueous alkaline solution; catechol borane; ammonia; thiourea;aluminum chlorohydrate; aluminum hydroxide; urea; iron hydroxide; ironchelates; tris(hydroxymethyl)nitromethane; brass or copper;acetylacetonate chelate of titanium; sodium percarbonate; erythorbicacid; lactone; serine; sodium methylate; and the sodium salt of laurylsarcosinate. Particularly preferred catalysts for use in the subjectcompositions are amine chelated brass, tris(hydroxymethyl)nitromethane,catechol borane, and sodium salt of lauryl sarcosinate.

Suitable reducing agents for use in the present invention include,without limitation, borohydrides such as sodium borohydride, lithium triethyl borohydride, or the like, aluminohydrides such as lithium aluminumhydride or the like. Although boro and alumino hydrides are preferred,any other reducing agent that does not interfere with the indicatedtransformations can also be used.

EXPERIMENTAL SECTION

General Synthetic Procedure

An primary alkyl amine is charged to a closed pressure reactor. Agreater than one molar excess of an aldehyde is then added slowly to theamine with stirring, while maintaining the temperature below the boilingpoint of the amine, generally between about 20° F. and about 110° F. Thetemperature is maintained by cooling the reactor during the aldehydeaddition process. The aldehyde addition can be incremental orcontinuous, but is performed at a rate that does not exceed the coolingcapacity of the reactor. Preferably, the aldehyde is added as a formal,such as methyl formal or butyl formal and in the case of formaldehyde asa inhibited solution in methanol.

Once aldehyde addition has been completed, the reaction temperature isallowed to rise to between about 90° F. and about 105° F. and thereaction is stirred at temperature for about 1 hour to about 24 hours.If excess aldehyde is still present, then the reaction can be subjectedto a digest step, where the temperature is raised to between about 140°F. and about 200° F.

After completion of the initial amine-aldehyde reaction, maintained atlow temperature to reduce dimer and trimer (triazine) production, adiamine or mixture of diamines is added to the reaction product keepingthe pH below about 12.5. The reaction is carried out between about 105°F. and about 121° F. for a period of time between about 4 and about 24hours. The reaction can also be performed with the addition of a smallamount of a formaldehyde or formaldehyde donor solution. If formaldehydeis used and not completely consumed, then an additional digest step canbe performed.

Example 1

This example illustrates the preparation of a substantially monomericamine-aldehyde starting material.

To an appropriately sized closed, pressurized reactor was charged 0.6074moles of a 40% solution of methylamine in water. 0.6073 moles of a 37%solution of formaldehyde in water (may also contain 7 to 25 wt. %methanol) was added slowly with stirring to the amine solution, whilemaintaining the temperature of about 40° F. during the addition bycooling the reactor. The addition is sufficiently slow so that thereactor cooling capacity can maintain the reaction near 40° F. Thereaction is then allowed to rise in temperature and stirred for 1 to 24hours. The amine-aldehyde adduct comprises substantially a bimolecularamine-aldehyde adduct, where the term substantially means ≧80 wt. % of abimolecular amine-aldehyde adduct, preferably, ≧85 wt. % of abimolecular amine-aldehyde adduct, particularly, ≧90 wt. % of abimolecular amine-aldehyde adduct and more and particularly, ≧95% of abimolecular amine-aldehyde adduct.

Example 2

This example illustrates the preparation of a diamine-terminated sulfurscavenger/converter composition that, although is effective as a sulfurscavenger under optimized conditions, does not have the thermalstability regarding the formation of detectable quantities of aldehydethat more preferred compositions of this invention possess.

Based on an hundred weight percent formulation, 98 wt. % of anamine-aldehyde product of Example 1 was charged to an appropriatelysized reactor. If the pH is above 10.5, then 1 wt. % of a 37% solutionof formaldehyde in methanol was added, otherwise no formaldehyde wasadded. After formaldehyde addition, if required, 1 wt. % of amine headswas added to the reactor at a temperature between about 105° F. andabout 121° F. for a period of time between about 4 and about 24 hours.After the reaction was complete, any imine was removed by hydrogenationwith sodium borohydride or a similar reducing agent. The final pH of thereaction mixture is between about 9 and about 13, with a pH betweenabout 10 and about 12.5 being preferred, depending on the amount ofdiamine added to the product of Example 1.

Example 3

the preparation of a diamine-terminated sulfur scavenger/convertercomposition that, although is effective as a sulfur scavenger underoptimized conditions, does not have the thermal stability regarding theformation of detectable quantities of aldehyde that more preferredcompositions of this invention possess.

To an appropriately sized reactor, 27828.08 lbs of a composition ofExample 1 was charged and 250 lbs of formaldehyde followed by 283 lbs ofamine heads. The reaction was stirred for 4 to 24 hours.

Example 4

This example illustrates the preparation of a preferreddiamine-terminated sulfur scavenger/converter composition using theinitial reaction product of Example 1 andN,N-bis(hydroxyethyl)ethylenediamine.

To an appropriately sized reactor, 393.69 gms of a composition ofExample 1 was charged. The composition had an initial pH of 11.44. Tothis composition was added step-wise addition of theN,N-bis(hydroxyethyl)ethylenediamine. The composition was stirred for1-4 hours and the pH measured after each incremental addition ofdiamine. Table I lists the total amount of diamine added, the wt % ratioand the pH after each addition. TABLE I Diamine Titration ofAmine-Aldehyde Adduct Total Amount Added (grams) pH wt. % 4.87 11.441.24 9.90 11.45 2.51 17.37 11.47 4.41 23.99 11.49 6.09 31.17 11.50 7.9238.23 11.52 9.71 45.57 11.53 11.58 52.76 11.55 13.40 59.92 11.56 15.2267.06 11.57 17.03 74.04 11.58 18.81 78.57 11.59 19.96

Example 5

This example illustrates the preparation of a preferreddiamine-terminated sulfur scavenger/converter composition using theinitial reaction product of Example 1 and Solutia Amine Heads (a mixtureof DCH, HMD and TMD).

To an appropriately sized reactor, 500.28 gms of a composition ofExample 1 was charged. The composition had an initial pH of 11.48. Tothis composition was added step-wise addition of the amine heads. Thecomposition was stirred for 1-4 hours and the pH measured after eachincremental addition of diamine heads. Table II lists the total amountof diamine heads added, the wt % ratio and the pH after each addition.TABLE II Diamine Titration of Amine-Aldehyde Adduct Total Amount Added(grams) pH wt. % 2.38 11.50 0.48 4.49 11.53 0.90 6.72 11.55 1.34 8.9211.59 1.78 11.05 11.61 2.21 13.28 11.63 2.65 15.62 11.65 3.12 17.9211.68 3.58 20.34 11.71 4.07 22.83 11.72 4.56 25.23 11.74 5.04 27.4311.76 5.48 29.67 11.77 5.93 31.79 11.78 6.35 33.78 11.79 6.75 35.8611.81 7.17

Example 6

This example illustrates the preparation of a preferreddiamine-terminated sulfur scavenger/converter composition using theinitial reaction product of Example 3 and hexamethylenediamine.

To an appropriately sized reactor, 400.00 gms of a composition ofExample 3 was charged. The composition had an initial pH of 10.46. Tothis composition was added step-wise addition of theN,N-bis(hydroxyethyl)ethylenediamine. The composition was stirred for1-4 hours and the pH measured after each incremental addition ofdiamine. Table III lists the total amount of diamine added, the wt %ratio and the pH after each addition. TABLE III Diamine Titration ofAmine-Aldehyde Adduct Total Amount Added (grams) pH wt. % 4.42 11.251.11 6.26 11.37 1.57 8.17 11.46 2.04 10.29 11.55 2.57 12.52 11.61 3.1314.85 11.67 3.71 16.99 11.72 4.25 19.21 11.76 4.80 21.58 11.80 5.48

Example 7

This example illustrates the aldehyde liberation in ppm of thecompositions of Examples 3-6 upon heating in a microwave oven using anEnvironmental Sensor Company's Z300 Sensor using the instructionsupplied by Environmental Sensor Company. The results are shown in TableIV. TABLE IV Aldehyde Liberation Test Upon Heating Time Weighted AverageComposition pH (neat) Formaldehyde Liberation Example 3 10.44 4.21 ppmfor 60 seconds Example 4 11.60 0.00 ppm for 30 seconds Example 5 12.010.00 ppm for 80 seconds Example 6 11.78 0.00 ppm for 80 seconds

Clearly, the results of the aldehyde liberation test indicate that byadjusting the amount of diamine added to the intermediate amine-aldehydereaction product of Example 1, sulfur scavengers that liberatesubstantially no detectable amount of formaldehyde can be prepared.These composition including a sufficient amount of diamine to suppressaldehyde liberation upon heating represent the preferred compositions ofthis invention from an environmental and health aspect. The compositionswithout the additional or optimized amount of diamine are acceptablesulfur scavengers for all applications, but do not have the preferredhigh temperature characteristics of the compositions of Examples 4-6.The compositions of Examples 4-6 are formed by reacting or contacting areaction product of Example 1 with an effective amount of a diamine toform a diamine terminated-amine/aldehyde composition, where theeffective amount of diamine is sufficient to reduce, reduce below adetectable level or substantially eliminate aldehyde liberation uponheating.

Noxious Sulfur Scavenging Data

Example 8

This example illustrates the effectiveness of the scavenger of Example 3used in systems or well located in the Lady Fern field in Canada over a21 week trial, where the amount and manner of introduction of thecomposition of Example 3 amount were optimized by adjusting the amountof composition to the amount of H₂S present in the well fluids and byincreasing the number of injection points for introducing thecomposition into the fluids. The test monitored water production,scavenger usage and other properties of the produced well fluids overthe 21 week trial.

Referring now to FIG. 1, total facility weekly cost ratios (cost/BOE)and water production comparison data is shown over the 21 week trialusing a composition of Example 3. The plot shows under initialconditions, facility water usage was up around 800 m³/day and cost/BOEwas about $0.40. The amount of composition was then optimized whichinvolved adding an excess of composition based on the amount of H₂S inthe fluids. It can be seen that optimization of compositionconcentration began to improve cost/BOE while water usage lagged. Theoptimization process continued where injection points were changed onwell #1. It is clear that optimization of the amount of compositionadded and changes in the injection points brought water usage down toabout 50 m³/day and cost was reduce to under $0.20.

Referring now to FIG. 2, a plot of weekly average location specificcost/BOE and associated water production data is shown over the 21 weektrial. Again, the data shows reductions in cost and water production forthe production facility and well #1.

Referring now to FIG. 3, a plot of composition weekly average usage(L/day) at specific locations. Again, the amounts of the composition ofthis invention and the 12″ water production were significantly reducedafter optimizing both the amount used and changing the injection pointsfor the facility and well #1.

Referring now to FIG. 4, a plot of the composition weekly average usageover the 21 week trial is shown. Again, the data shows a drop from over1400 L/day at the start of the trial to a rate of about 100 L/day afteroptimization of both the amount used and the points of injection.

Referring now to FIG. 5, a plot of weekly averages of composition usage,12″ line production and L/MMSCF is shown. Again, the data showedsignificant reductions in composition usage and in L/MMSCF ratio and amodest reduction in 12″ line production.

Referring now to FIG. 6, a plot of total scavenger usage (average weeklyL/day) is shown. Again, the initial usage was at about 2000 L/Day beforeoptimization and was reduced to below about 750 L/day afteroptimization.

Referring now to FIG. 7, a plot of total facility average L/MMSCF ratiois shown. Again, the data showed a significant reduction in scavengerusage (L/MMSCF) over the 21 week trial from an initial value of about 35L/MMSCF to about 15 L/MMSCF after amount and injection pointoptimization.

The testing data clearly evidences that the compositions of thisinvention a effective scavengers for application in cold climates andare well suited for partitioning in a tri-phasic environment providingcost effective noxious sulfur species removal.

All references cited herein are incorporated by reference. While thisinvention has been described fully and completely, it should beunderstood that, within the scope of the appended claims, the inventionmay be practiced otherwise than as specifically described. Although theinvention has been disclosed with reference to its preferredembodiments, from reading this description those of skill in the art mayappreciate changes and modification that may be made which do not departfrom the scope and spirit of the invention as described above andclaimed hereafter.

1. A sulfur scavenging composition comprising a diamine terminatedreaction product of at least one aldehyde with at least one primaryamine, where the reaction product includes substantially bimolecularamine-aldehyde adducts.
 2. The composition of claim 1, wherein thecomposition includes a sufficient amount of the diamine to substantiallyeliminate aldehyde liberation upon heating.
 3. The composition of claim1, wherein the reaction product is substantially free of higheraldehyde-amine adducts.
 4. The composition of claim 3, wherein thehigher aldehyde-amine adducts are selected from the dimers, trimers,triazines and mixtures thereof.
 5. The composition of claim 1, whereinthe primary amines are selected from the group consisting of amines ofthe general formula:R″NH₂ where R″ is a linear or branched alkyl, aryl, alkaryl, or aralkylgroup having between about 1 and about 20 carbon atoms and where one ormore of the carbon atoms can be oxygen atoms in the form of carboxy,hydroxy and/or ether moieties and/or nitrogen atoms can be in the formof tertiary amine or amide moieties, and one or more of the hydrogenatoms can be replaced by a fluorine atom or chlorine atom.
 6. Thecomposition of claim 1, wherein the aldehydes are selected from thegroup consisting of aldehydes of the general formula:R′—CHO or aldehyde donors that generate such aldehydes, where R′ is ahydrogen atom (H) or a linear or branched alkyl, aryl, alkaryl, oraralkyl group having between about 1 and about 20 carbon atoms and whereone or more of the carbon atoms can be oxygen atoms in the form ofcarboxy, hydroxy and/or ether moieties and/or nitrogen atoms can be inthe form of tertiary amine or amide moieties, and where one or more ofthe hydrogen atoms can be replaced by fluorine atoms and/or chlorineatoms.
 7. The composition of claim 1, wherein the aldehydes are selectedfrom the group consisting of the general formula:R′—CHO or aldehyde donors that generate such aldehydes, where R′ isselected from the group consisting of H, methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, isobutyl, hexyls (linear or branched),hepyls, octyls, nonyls, decyls, phenyl, benzyl, methyl substitutedphenyls, and mixtures or combinations thereof.
 8. The composition ofclaim 1, wherein the aldehydes are selected from the group consisting offormaldehyde, paraformaldehyde, arylaldehydes, methoxyaldehydes,hydroxyaldehydes or aldols, glyceraldehydes, vanillin, veratraldehyde,alloxan, noneal, 1-formyl piperdine, salicylaldehyde, citronella andmixtures or combinations thereof.
 9. The composition of claim 1, whereinthe aldehydes are selected from the group consisting ofparaformaldehyde, paraldehyde, formaldehyde, acetaldehyde,glycolaldehyde, glyceraldehyde, hydroxymethyl glyceraldehyde, glyoxal,and methyl formcel (a hemi-acetal, 55 percent formaldehyde solution inmethanol and methoxy-methanol or water), aldols, and mixtures orcombinations thereof.
 10. The composition of claim 1, wherein thediamines are selected from the group consisting of diamines of thegeneral formulaH₂N—R—NH₂R where R is linear or branched alkenyl groups having betweenabout 1 and about 20 carbon atoms, cycloalkenyl groups having betweenabout 1 and about 20 carbon atoms, alkylcycloalkenyl groups havingbetween about 1 and about 20 carbon atoms, alka arenyl group havingbetween about 1 and about 20 carbon atoms, ara alkenyl group havingbetween about 1 and about 20 carbon atoms and mixtures or combinationsthereof, where one or more of the carbon atoms can be oxygen atoms inthe form of carboxy, hydroxy and/or ether moieties and/or nitrogen atomscan be in the form of tertiary amine or amide moieties, and where one ormore of the hydrogen atoms can be replaced by fluorine atoms and/orchlorine atoms.
 11. The composition of claim 1, wherein the primaryamine is methyl amine, the aldehyde is formaldehyde and the diamine isamine heads.
 12. A composition for converting noxious sulfur species tohigh molecular weight sulfur species comprising at least one compound offormula (I):

where R is an alkenyl group, cycloalkenyl or arenyl group having betweenabout 1 and about 20 carbon atoms, where one or more of the carbon atomscan be oxygen atoms in the form of carboxy, hydroxy and/or ethermoieties and/or nitrogen atoms can be in the form of tertiary amine oramide moieties, R′ and R″ are the same or different carbon-containinggroups having between about 1 and about 20 carbon atoms, where one ormore of the carbon atoms can be oxygen atoms in the form of carboxy,hydroxy and/or ether moieties or nitrogen atoms in the form of tertiaryamine and/or nitrogen-containing groups in the form of amide moietiesand where k, l, m and n are integers having a value between 0 and 2,provided that at least one has a value of 1 or
 2. 13. The composition ofclaim 12, wherein the composition includes a sufficient amount of thediamine to substantially eliminate the liberation of aldehyde uponheating and where the reaction product includes substantially no higheraldehyde-amine adducts.
 14. The composition of claim 12, wherein R″ is amethyl group, R′ is H, and R is an cycloalkenyl group associated withdiamines in amine heads.
 15. A method for preparing sulfur scavengingcompositions including the steps of: contacting at least one aldehydewith at least one primary amine under conditions to form a reactionproduct comprising substantially bimolecular adducts of the amines andthe aldehydes having substantially no trimer or triazine adducts; andcontacting the reaction product with at least one diamine to form afinal reaction product comprising at least one compound of formula (I):

where R is an alkenyl group, cycloalkenyl or arenyl group having betweenabout 1 and about 20 carbon atoms, where one or more of the carbon atomscan be oxygen atoms in the form of carboxy, hydroxy, and/or ethermoieties and/or nitrogen atoms in the form of tertiary amine and/oramide moieties, R′ and R″ are the same or different carbon-containinggroups having between about 1 and about 20 carbon atoms, where one ormore of the carbon atoms can be oxygen atoms in the form of carboxy,hydroxy and/or ether moieties or nitrogen atoms in the form of tertiaryamine and/or nitrogen-containing groups in the form of amide moietiesand where k, l, m and n are integers having a value between 0 and 2,provided that at least one has a value of 1 or
 2. 16. The method ofclaim 15, wherein the diamine is added in an amount sufficient tosubstantially eliminate aldehyde liberation upon heating.
 17. The methodof claim 15, further comprising the step of: contacting the finalreaction product with a reducing agent to convert any imine by-productsin the final reaction product to their corresponding saturated analogs.18. The method of claim 17, wherein the reducing agent is sodiumborohydride.
 19. The method of claim 15, wherein R″ is a methyl group,R′ is H, and R is an cycloalkenyl group associated with diamines inamine heads.
 20. (canceled)
 21. (canceled)
 22. (canceled)
 23. (canceled)24. (canceled)
 25. (canceled)
 26. (canceled)
 27. (canceled) 28.(canceled)
 29. (canceled)
 30. (canceled)
 31. (canceled)
 32. (canceled)33. (canceled)
 34. (canceled)
 35. (canceled)
 36. (canceled) 37.(canceled)
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 40. (canceled)
 41. (canceled)42. (canceled)
 43. (canceled)
 44. (canceled)
 45. A sulfur scavengingcomposition comprising a diamine terminated reaction product of at leastone aldehyde with at least one primary amine, where the reaction productincludes substantially bimolecular amine-aldehyde adducts, where asufficient amount of diamine is used to substantially eliminate aldehydeliberation upon heating and where the reaction product is substantiallyfree of higher aldehyde-amine adducts.
 46. The composition of claim 45,wherein the higher aldehyde-amine adducts are selected from the dimers,trimers, triazines and mixtures thereof.
 47. A composition forconverting noxious sulfur species to high molecular weight sulfurspecies comprising at least one compound of formula (I):

where R is an alkenyl group, cycloalkenyl or arenyl group having betweenabout 1 and about 20 carbon atoms, where one or more of the carbon atomscan be oxygen atoms in the form of carboxy, hydroxy and/or ethermoieties and/or nitrogen atoms can be in the form of tertiary amine oramide moieties, R′ and R″ are the same or different carbon-containinggroups having between about 1 and about 20 carbon atoms, where one ormore of the carbon atoms can be oxygen atoms in the form of carboxy,hydroxy and/or ether moieties or nitrogen atoms in the form of tertiaryamine and/or nitrogen-containing groups in the form of amide moietiesand where k, l, m and n are integers having a value between 0 and 2,provided that at least one has a value of 1 or 2 and where a sufficientamount of diamine is used to substantially eliminate the liberation ofaldehyde upon heating and the composition includes substantially nohigher aldehyde-amine adducts.
 48. The composition of claim 45, whereinthe composition includes a sufficient amount of the diamine tosubstantially eliminate aldehyde liberation upon heating.
 49. Thecomposition of claim 45, wherein the primary amines are selected fromthe group consisting of amines of the general formula:R″NH₂ where R″ is a linear or branched alkyl, aryl, alkaryl, or aralkylgroup having between about 1 and about 20 carbon atoms and where one ormore of the carbon atoms can be oxygen atoms in the form of carboxy,hydroxy and/or ether moieties and/or nitrogen atoms can be in the formof tertiary amine or amide moieties, and one or more of the hydrogenatoms can be replaced by a fluorine atom or chlorine atom.
 50. Thecomposition of claim 45, wherein the aldehydes are selected from thegroup consisting of aldehydes of the general formula:R′—CHO or aldehyde donors that generate such aldehydes, where R′ is ahydrogen atom (H) or a linear or branched alkyl, aryl, alkaryl, oraralkyl group having between about 1 and about 20 carbon atoms and whereone or more of the carbon atoms can be oxygen atoms in the form ofcarboxy, hydroxy and/or ether moieties and/or nitrogen atoms can be inthe form of tertiary amine or amide moieties, and where one or more ofthe hydrogen atoms can be replaced by fluorine atoms and/or chlorineatoms.
 51. The composition of claim 45, wherein the aldehydes areselected from the group consisting of the general formula:R′—CHO or aldehyde donors that generate such aldehydes, where R′ isselected from the group consisting of H, methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, isobutyl, hexyls (linear or branched),hepyls, octyls, nonyls, decyls, phenyl, benzyl, methyl substitutedphenyls, and mixtures or combinations thereof.
 52. The composition ofclaim 45, wherein the aldehydes are selected from the group consistingof formaldehyde, paraformaldehyde, arylaldehydes, methoxyaldehydes,hydroxyaldehydes or aldols, glyceraldehydes, vanillin, veratraldehyde,alloxan, noneal, 1-formyl piperdine, salicylaldehyde, citronella andmixtures or combinations thereof.
 53. The composition of claim 45,wherein the aldehydes are selected from the group consisting ofparaformaldehyde, paraldehyde, formaldehyde, acetaldehyde,glycolaldehyde, glyceraldehyde, hydroxymethyl glyceraldehyde, glyoxal,and methyl formcel (a hemi-acetal, 55 percent formaldehyde solution inmethanol and methoxy-methanol or water), aldols, and mixtures orcombinations thereof.
 54. The composition of claim 45, wherein thediamines are selected from the group consisting of diamines of thegeneral formulaH₂N—R—NH₂R where R is linear or branched alkenyl groups having betweenabout 1 and about 20 carbon atoms, cycloalkenyl groups having betweenabout 1 and about 20 carbon atoms, alkylcycloalkenyl groups havingbetween about 1 and about 20 carbon atoms, alka arenyl group havingbetween about 1 and about 20 carbon atoms, ara alkenyl group havingbetween about 1 and about 20 carbon atoms and mixtures or combinationsthereof, where one or more of the carbon atoms can be oxygen atoms inthe form of carboxy, hydroxy and/or ether moieties and/or nitrogen atomscan be in the form of tertiary amine or amide moieties, and where one ormore of the hydrogen atoms can be replaced by fluorine atoms and/orchlorine atoms.
 55. The composition of claim 45, wherein the primaryamine is methyl amine, the aldehyde is formaldehyde and the diamine isamine heads.
 56. The composition of claim 47, wherein the compositionincludes a sufficient amount of the diamine to substantially eliminatealdehyde liberation upon heating.
 57. The composition of claim 47,wherein the higher aldehyde-amine adducts are selected from the dimers,trimers, triazines and mixtures thereof.
 58. The composition of claim47, wherein the primary amines are selected from the group consisting ofamines of the general formula:R′NH₂ where R″ is a linear or branched alkyl, aryl, alkaryl, or aralkylgroup having between about 1 and about 20 carbon atoms and where one ormore of the carbon atoms can be oxygen atoms in the form of carboxy,hydroxy and/or ether moieties and/or nitrogen atoms can be in the formof tertiary amine or amide moieties, and one or more of the hydrogenatoms can be replaced by a fluorine atom or chlorine atom.
 59. Thecomposition of claim 47, wherein the aldehydes are selected from thegroup consisting of aldehydes of the general formula:R′—CHO or aldehyde donors that generate such aldehydes, where R′ is ahydrogen atom (H) or a linear or branched alkyl, aryl, alkaryl, oraralkyl group having between about 1 and about 20 carbon atoms and whereone or more of the carbon atoms can be oxygen atoms in the form ofcarboxy, hydroxy and/or ether moieties and/or nitrogen atoms can be inthe form of tertiary amine or amide moieties, and where one or more ofthe hydrogen atoms can be replaced by fluorine atoms and/or chlorineatoms.
 60. The composition of claim 47, wherein the aldehydes areselected from the group consisting of the general formula:R′—CHO or aldehyde donors that generate such aldehydes, where R′ isselected from the group consisting of H, methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, isobutyl, hexyls (linear or branched),hepyls, octyls, nonyls, decyls, phenyl, benzyl, methyl substitutedphenyls, and mixtures or combinations thereof.
 61. The composition ofclaim 47, wherein the aldehydes are selected from the group consistingof formaldehyde, paraformaldehyde, arylaldehydes, methoxyaldehydes,hydroxyaldehydes or aldols, glyceraldehydes, vanillin, veratraldehyde,alloxan, noneal, 1-formyl piperdine, salicylaldehyde, citronella andmixtures or combinations thereof.
 62. The composition of claim 47,wherein the aldehydes are selected from the group consisting ofparaformaldehyde, paraldehyde, formaldehyde, acetaldehyde,glycolaldehyde, glyceraldehyde, hydroxymethyl glyceraldehyde, glyoxal,and methyl formcel (a hemi-acetal, 55 percent formaldehyde solution inmethanol and methoxy-methanol or water), aldols, and mixtures orcombinations thereof.
 63. The composition of claim 47, wherein thediamines are selected from the group consisting of diamines of thegeneral formulaH₂N—R—NH₂R where R is linear or branched alkenyl groups having betweenabout 1 and about 20 carbon atoms, cycloalkenyl groups having betweenabout 1 and about 20 carbon atoms, alkylcycloalkenyl groups havingbetween about 1 and about 20 carbon atoms, alka arenyl group havingbetween about 1 and about 20 carbon atoms, ara alkenyl group havingbetween about 1 and about 20 carbon atoms and mixtures or combinationsthereof, where one or more of the carbon atoms can be oxygen atoms inthe form of carboxy, hydroxy and/or ether moieties and/or nitrogen atomscan be in the form of tertiary amine or amide moieties, and where one ormore of the hydrogen atoms can be replaced by fluorine atoms and/orchlorine atoms.
 64. The composition of claim 47, wherein the primaryamine is methyl amine, the aldehyde is formaldehyde and the diamine isamine heads.